CN106915735A - A kind of preparation method of nitrogen or metal-doped carbon material - Google Patents
A kind of preparation method of nitrogen or metal-doped carbon material Download PDFInfo
- Publication number
- CN106915735A CN106915735A CN201710056827.8A CN201710056827A CN106915735A CN 106915735 A CN106915735 A CN 106915735A CN 201710056827 A CN201710056827 A CN 201710056827A CN 106915735 A CN106915735 A CN 106915735A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- preparation
- carbon material
- room temperature
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of nitrogen or the preparation method of metal-doped carbon material, comprising following operating procedure：(1) 2,6 diacetyl pyridines and the amino monomers of 2 or more than 2 are used, under conditions of solvent, catalyst and inert gas shielding, reaction forms iminopyridine ligand polymer；(2) step (1) gained iminopyridine ligand polymer is carried out into thermal cracking treatment under inert gas shielding, obtains nitrogen-doped carbon material, post-processed, obtained final product.The present invention prepares gained nitrogen or the preparation method of metal-doped carbon material accounts for 0.5%~10% containing weight nitroxide, and it is 29~57%, product BET about 300m that the yield of product is obtained after thermal cracking polymer2/ g to 1500m2/ g, shows big capacitive characteristics during as super capacitor, during as electrode material of lithium battery, show good storage lithium performance and stable circulation performance.
Description
Technical field
The invention belongs to electrochemical energy field of material technology, and in particular to the preparation of a kind of nitrogen or metal-doped carbon material
Method.
Background technology
Carbon is that nature is originated one of most commonly used element, there are various allotrope types, structure from it is one-dimensional to
It is three-dimensional.Carbon is a kind of preferable matrix material, and with low cost, electric conductivity is good, and specific surface area is big, structure and good stability etc.
Advantage and be widely used in energy and material, medical material, catalysis material.For N doping material, nitrogen-atoms is more former than carbon
Sub many valence electrons, the incorporation of nitrogen-atoms changes the electronic structure and band gap of carbon atom around, makes the conduction of carbon material
Form changes so that free carrier quantity increases；N doping can form pyridine type, Bi Kaxing after entering six-membered ring structure
And the nitrogen-containing functional group such as graphite mould, these functional groups can improve carbon material surface activity, also its electronic structure can be adjusted,
And the size and electronegativity of nitrogen-atoms are different from carbon atom, the rearrangement of electric charge is caused and because of doping in material internal
The crystal defect for causing.Meanwhile, foreign atom can cause spin reallocation so as to produce new more excellent physicochemical property, can make
It is the active sites with adsorbing metal atom ability, the interaction between enhancing metallic atom and carbon atom.So, nitrogen carbon doping
The research of aspect has attracted the sight of numerous scientific workers.
The nitrating carbon material of research is mainly used in the fields such as fuel cell, lithium ion battery and ultracapacitor at present.
Application of the nitrating carbon material in terms of ultracapacitor also result in the extensive concern of people, and super capacitor is a kind of novel energy-storing
Device, its specific energy is big, and light weight, efficiency for charge-discharge is high, and can discharge and recharge often, compared with secondary cell, with power
It is higher, the more preferable advantage of cyclical stability, and nitrating carbon material has conductance high, specific surface area is big, and corrosion resistance is good, surely
Qualitative good the advantages of.Nitrating carbon material is applied to ultracapacitor, nitrogen-atoms is easily entered in carbon material, nitrogen-atoms is mixed
Entering can increase electric capacity as electron donor, can also soak carbon material.Electric double layer area can be increased in super capacitor, increase electricity
The energy stores of container, and compatibility is good, is a kind of outstanding ultracapacitor battery material, such as electrodeposition process prepares polyphenyl
Amine nanofiber, prepares nitro-carbide in ultracapacitor, hence it is evident that improve electric capacity and conductance, be widely used at present
Nitrating carbon material has nitrating activated carbon and nitrogen-doped graphene.
Nitrating carbon material is general to be present in activated carbon in the form of the chemical nitrogen and structure nitrogen, and chemical nitrogen is present in charcoal table
Face, exists with amino, nitroso form, and structure nitrogen is in occupation of carbon skeleton position.The preparation method one of nitrogen-doped carbon material
As have nitriding in situ, post treatment method and direct synthesis technique [Adv.Funct.Mater., 2012,22,1069.].Nitrating in situ
Method be using rich nitrogen presoma as nitrogen source and carbon source, such as from polypyrrole, polyaniline high polymer and glucose, sucrose etc.,
When using gas acetonitrile, with chemical vapour deposition technique or template be obtained porous structure material [Nature, 2010,468,
549.].Post treatment method is that nitrogen source is mixed when possessing carbon source, such as introduces ammonia, ethylenediamine nitrogen-enriched compounds, is led to during post processing
Overheating Treatment method, plasma processing method and hydrazine hydrate facture are obtained.As nitrogen-atoms it is graphene-doped in, with pyridine nitrogen, pyrrole
Cough up nitrogen and graphite nitrogen form is present.Direct synthesis technique such as chemical vapour deposition technique [ACS Nano, 2012,6,5259.], is in silicon
Adhere to copper on substrate, chemical vapor deposition obtains nitrogen-doped graphene under the atmosphere of 800 DEG C of hydrogen.Isolation growth method, solvent heat
Method, such as using urea as nitrogen source, after mixing with graphene oxide liquid phase, freeze-drying water removal, through 600 DEG C under inert gas atmosphere
It is thermally treated resulting in nitrogen-doped graphene [Adv.Ener.Mater., 2012,2 (7):884-888.].Arc discharge method, in hydrogen and
Arc discharge is carried out in nitrogen source atmosphere, between carbon electrode obtain nitrating carbon material.Other also have Plasma discharge methods, in ammonia
Lower heating using microwave graphite, obtains nitrogen-doped graphene.
Nitrating carbon material such as macrocyclic compound Cobalt Phthalocyanine, phthalein cyanogen iron is the macrocyclic compound with cobalt, iron as metal center,
Show excellent ORR catalysis activities in Proton Exchange Membrane Fuel Cells, but its central metal carrying capacity, heat treatment process, nitrogen
Source Type, and used carrier influences larger [Science, 2015,6257,185-189.] to catalyst performance.Nitrogenous coalescence
When the carbon-based cobalt doped catalyst that imidazoles is prepared for nitrogen source, conducting polymer such as polypyrrole, polyaniline etc. are used as catalyst, catalysis is lived
Property is not high, and catalysis activity continuous decrease over time, is routinely incorporated into transition metal, obtains transition metal and foreign atom oxygen also
Former activated centre [CN103296292A].Metal-nitrogen-carbon type catalyst is prepared, can be by chemical vapor deposition, sol-gel
Method, low temperature plasma carbonizatin method, ultrasonic spray pyrolysis, microwave method etc..As chemistry polymerizing in situ method synthesizes polypyrrole bag
Carbon mano-tube composite is covered, complexed transition metal prepares surface area high, the oxygen reduction catalyst of many avtive spots.
In recent years, it was recently reported that many on nitrating carbon material, the application obtained in electrochemistry.Carbon material is with a kind of carrier
Form occur, itself can not provide more avtive spots, typically prepare non-precious metal catalyst by matrix of carbon material.
Porous carbon materials or organic metal gel are such as used, by mixing double bigcatkin willows contracting ethylenediamine cobalt [CN100461511C], Bi Kahe
Iron chloride, p-methyl benzenesulfonic acid [CN102614915A], 2- (2- pyridines)-benzimidazoles prepare [CN104138759A] for nitrogen source,
But this kind of catalyst structure less stable, specific surface area is low, and price is high.It is nitrogen source such as to use 2'2- bipyridyls, is received with carbon
Mitron ultrasonic mixing, adds that slaine is thermally treated obtains catalyst, but preparation cost is [CN102698755A] high.Using graphite
Alkene material or acetylene black are carbon-based supports, melamine or hexamethylenetetramine are mixed as nitrogen source, after mechanical mixture heat treatment
Nitrating carbon-supported catalysts are obtained, its poor durability, nitrogen content is low, active sites are few [CN101859906B].Use carbon containing nitrogen
High polymer monomer be presoma, polymerization form macromolecular compound, be complexed to be formed centered on metal with slaine, be similar to
The trigonal biyramid configuration of the symmetrical distortions of Cs, an equatorial plane is constituted with N2 (pyridine) and anion 1 and anion 2, N1 and
N3 is located at the complex structure material [WO 2010/030237A1] of axial position, is applied to homogeneous catalysis and during multiphase urges field.
We use this kind of precursor synthesis technology, through carbonization and post processing after, first explore be applied in electrochemical material field.This
Class synthetic material possesses good electric conductivity after carbonization, and stability, specific surface area high, surface defect is more, and it is excellent that wetability is good etc.
Gesture.
The information for being disclosed in the background section is merely intended to increase the understanding to general background of the invention, without answering
In being considered as recognizing or imply in any form that the information structure has been the prior art well known to persons skilled in the art.
The content of the invention
The present invention invents the preparation side of a kind of nitrogen or metal-doped carbon material for technical problem present in prior art
Method, it is intended to obtain one kind and possess the advantages of good electric conductivity, stability, high-specific surface area, surface defect are more, wetability is good, and
Its low in raw material price, preparation method are simple, can be mass-produced, and can be widely used in the nitrogen or metal of electrochemical material field
The preparation method of doping carbon material.
To achieve the above object, the technical scheme that the present invention is provided is as follows：
The preparation method of a kind of nitrogen or metal-doped carbon material, comprising following operating procedure：
(1) DAP and the amino monomers of 2 or more than 2 are used, in solvent, catalyst and indifferent gas
Under conditions of body protection, there is dehydrating condensation in reaction, acyl group with amino, form many flute profiles with metal ion complexation ability sub-
Aminopyridine ligand polymer；
(2) step (1) gained iminopyridine ligand polymer is carried out into thermal cracking treatment under inert gas shielding,
Nitrogen-doped carbon material is obtained, is post-processed, obtained final product.
Wherein, to prepare metal-nitrogen co-doped carbon material, also including following operation：To step (1) gained imino group
Slaine is added in pyridine ligand polymer carries out mixed ligand, forms the polymer with metal ion, is dried to obtain metal
Ionic polymer powder；Wherein, described solvent is identical with the solvent described in step (1)；Metal ion will be dried to obtain to gather
Compound powder carries out thermal cracking treatment under mixed gas protected, obtains metal-nitrogen co-doped carbon material.
Wherein, the metal ion in pyridine ligand mole and slaine in described iminopyridine ligand polymer
The ratio between mole be 1：1~2；Described drying temperature is 80~100 DEG C, is dried 8~12 hours.
Wherein, described slaine is iron, cobalt, nickel, the chloride of manganese plasma compound, nitrate, sulfate or vinegar
Hydrochlorate one or more mixtures.
Wherein, the solvent described in step (1) is methyl alcohol, ethanol, n-butanol, propyl alcohol, water, dimethyl sulfoxide (DMSO), dimethyl
One or more in formamide, dimethylacetylamide, monochloro methane, dichloromethane, chloroform or tetrachloromethane are mixed
Compound；Described catalyst is the one kind in formic acid, acetic acid or oxalic acid；Described inert gas is conjunction nitrogen, argon gas or helium
In one kind.
Wherein, reaction temperature is 50 DEG C~150 DEG C in step (1), and the reaction time is 8~24 hours, is continued during reaction
Stirring.
Wherein, described in step (1) DAP and the amino monomers of 2 or more than 2 are into mol ratio
1:0.8~1.2.
Wherein, the amino monomers described in step (1) are 2,6- diaminopurines, 6- methyl -2,4- pyrimidinediamines, 2,4-
Di-amino-pyrimidine, 1,5- naphthylenediamines, DAP, benzidine, p-phenylenediamine, melamine, 1,8- diaminos
Base naphthalene, 4- diazanyls -6- (2- pyridines) -1,3,5-triazines -2- amine, the methyl isophthalic acid of 2,4- diaminourea -6,3,5- triazines, 2,3,5,6- tetra-
Aminopyridine hydrochloride, -6 phenyl of 2,4- diaminourea -1,3,5-triazines, 2,4- diaminourea -6- dimethylaminos -1,3,5-triazines,
4,6- tri- ammonia -1,3,5-triazines, 2,4- diamino-1,3,5-triazines, 2,4- di-amino-pyrimidine -5- nitriles, Isosorbide-5-Nitrae-cyclohexanediamine or
One kind in 2,6- diaminopyrazines.
Wherein, thermal cracking treatment temperature described in step (2) is to keep heating rate for 5~10 DEG C/min is warming up to 650
~1050 DEG C of high temperature cabonizations 1~2 hour；Mixed gas described in step (2) are inert gas or inert gas and ammonia
Mixture, described inert gas is the one kind in nitrogen, argon gas or helium；Described inert gas is with ammonia according to 1:
0.2 volume ratio mixes.
Wherein, the post processing described in step (2) includes pickling, cooling, separation, cleaning, 80~100 DEG C of dryings 8 hours
More than, secondary thermal cracking treatment is then carried out, process time is 0.5~2 hour, and temperature is 400~600 DEG C, that is, obtain product；
Wherein, described pickling uses the sulfuric acid solution keeping temperature that concentration is 0.5mol/L to be 80~100 DEG C and cleans 8~12 hours,
Room temperature is cooled to, after filtering, is cleaned with deionized water more than 8 times, or it is the hydrochloric acid solution room of 0.1mol/L to use concentration
The lower cleaning of temperature 12 hours, is cooled to room temperature, after filtering, is cleaned with deionized water more than 8 times.
Compared with prior art, the present invention has the advantages that：
The present invention prepares gained nitrogen or the preparation method of metal-doped carbon material accounts for 0.5%~10% containing weight nitroxide,
It is 29~57%, product BET about 300m that the yield of product is obtained after thermal cracking polymer2/ g to 1500m2/ g, as super capacitor
When show big capacitive characteristics, during as electrode material of lithium battery, show good storage lithium performance and stable circulation performance,
During as fuel battery cathode with proton exchange film catalyst, good O is showed2Reducing activity, anti-CO toxicity is good, and oxidizing process is
4 electronic processes, good catalysis activity is shown in the anode and negative electrode of Proton Exchange Membrane Fuel Cells, is promised to be
Electro Catalysts for PEMFC of new generation；Further, product of the present invention has low cost, and activity is high, stablizes,
The feature such as can be mass-produced.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram that the present invention prepares products obtained therefrom.
Fig. 2 present invention prepares the transmission electron microscope picture (a) and (b) of products obtained therefrom, high-resolution-ration transmission electric-lens figure (c) and (d).
Fig. 3 present invention prepares the cyclic voltammetry curve under the oxygen saturation of products obtained therefrom.
Fig. 4 present invention prepares the polarization curve under the oxygen saturation of products obtained therefrom.
Fig. 5 present invention prepares the cyclic voltammetry curve under the oxygen saturation of products obtained therefrom.
Fig. 6 present invention prepares the polarization curve under the oxygen saturation of products obtained therefrom.
Fig. 7 present invention prepares the graph of pore diameter distribution of products obtained therefrom.
Fig. 8 present invention prepares cyclic curve when products obtained therefrom is applied to prepare lithium electricity electrode.
Fig. 9 present invention prepares the cyclic voltammetry curve under the oxygen saturation of products obtained therefrom.
Figure 10 present invention prepares cyclic voltammetry curve when products obtained therefrom is applied to prepare electric capacity.
Specific embodiment
Specific embodiment is described in detail below in conjunction with the accompanying drawings, it is to be understood that protection scope of the present invention is not received
The limitation of specific embodiment.
Embodiment 1
A kind of preparation method of metal-nitrogen-doped carbon material, operating procedure is as follows：
(1) ethanol solution for taking 50ml is placed in two mouthfuls of flasks equipped with condensation return pipe, adds 2,6- diacetyls
Pyridine 1mol, is stirred at room temperature 10 minutes, adds p-phenylenediamine 1mol, is stirred at room temperature 10 minutes, under nitrogen protection, from room temperature
After being heated to 100 DEG C, oxalic acid 0.1g is added, continue stirring reaction 24 hours, acyl group occurs dehydration contracting with amino in course of reaction
Close, form many flute profile iminopyridine ligand polymers with metal ion complexation ability, naturally cool to room temperature；
(2) anhydrous frerrous chloride 0.5mol is taken, is dissolved in 10ml absolute ethyl alcohols, ferrous iron to be chlorinated is completely dissolved completely,
Disposable being dissolved with during the 10ml ethanol solutions of anhydrous frerrous chloride are added to step (1) contains iminopyridine part
In two mouthfuls of flasks of polymer, reaction 12 hours is stirred at room temperature, forms the polymer with metal ion, resulting solution will be reacted
It is placed in forced air drying, after 80 DEG C of dryings 5 hours, is placed in vacuum drying chamber, 80 DEG C of dryings 10 hours obtains metal ion and gather
Compound powder；
(3) step (2) gained metal ion polymer powder is ground 10 minutes, being subsequently placed in tube furnace carries out hot tearing
Solution treatment, that is, after being passed through nitrogen 30 minutes, 850 DEG C are heated to from room temperature with 5 DEG C/min, are incubated 2 hours, naturally cool to room
Temperature；Gained material is taken out into grinding 10 minutes, is put into the 0.5mol/L sulfuric acid solutions of 500ml, 80 DEG C of stirrings are carried out for 10 hours
Pickling, is cooled to room temperature, and suction filtration is separated, and is cleaned with deionized water more than 8 times, 100 DEG C of dryings 12 hours in vacuum drying chamber,
Being placed in again in tube furnace carries out secondary thermal cracking treatment, after being passed through nitrogen 30 minutes, 500 is heated to 5 DEG C/min from room temperature
DEG C, process 1 hour, naturally cool to room temperature and obtain product, as metal-nitrogen-doped carbon material.
Products obtained therefrom is done into X-ray diffraction, gained collection of illustrative plates is as shown in Figure 1：Very strong graphitic carbon is shown in figure as shown in Figure 1
Peak and Fe3C peaks, show that metal-nitrogen co-doped carbon material is a kind of carbon-based material for mixing iron.
Products obtained therefrom is done into transmission electron microscope picture, gained collection of illustrative plates is as shown in Figure 2：It can be seen that ferrous metal particle
Particle diameter is less than 80nm, forms clad structure, is uniformly distributed.
Embodiment 2
A kind of preparation method of metal-nitrogen-doped carbon material, operating procedure is as follows：
(1) butanol solution for taking 50ml is placed in two mouthfuls of flasks equipped with condensation return pipe, adds 2,6- diacetyl pyrroles
Pyridine 1mol, is stirred at room temperature 20 minutes, adds melamine 1mol, is stirred at room temperature 20 minutes, under argon gas gas shielded, from room temperature
After being heated to 110 DEG C, oxalic acid 0.1g is added, continue stirring reaction 24 hours, acyl group occurs dehydration contracting with amino in course of reaction
Close, form many flute profile iminopyridine ligand polymers with metal ion complexation ability, naturally cool to room temperature；
(2) take without CoCL2 6H2O 1mol, be dissolved in 10ml n-butanols, cobalt to be chlorinated is completely dissolved completely, disposably
The 10ml butanol solutions of cobalt chloride will be dissolved with and be added to two mouthfuls of burnings containing iminopyridine ligand polymer in step (1)
In bottle, reaction 12 hours is stirred at room temperature, forms the polymer with metal ion, reaction resulting solution is placed in forced air drying
In, after 110 DEG C of dryings 5 hours, it is placed in vacuum drying chamber, 120 DEG C of dryings 10 hours obtain metal ion polymer powder；
(3) step (2) gained metal ion polymer powder is ground 20 minutes, being subsequently placed in tube furnace carries out hot tearing
Solution treatment, that is, after being passed through argon gas 30 minutes, 800 DEG C are heated to from room temperature with 5 DEG C/min, are incubated 2 hours, naturally cool to room
Temperature；Gained material is taken out into grinding 10 minutes, is put into the 0.5mol/L sulfuric acid solutions of 500ml, 80 DEG C of stirrings are carried out for 10 hours
Pickling, is cooled to room temperature, and suction filtration is separated, and is cleaned with deionized water more than 8 times, 120 DEG C of dryings 12 hours in vacuum drying chamber,
Being placed in again in tube furnace carries out secondary thermal cracking treatment, after being passed through argon gas 30 minutes, 600 is heated to 5 DEG C/min from room temperature
DEG C, process 2 hours, naturally cool to room temperature and obtain product, as metal-nitrogen-doped carbon material.
Fig. 5 is metal-nitrogen-doped carbon material that example 2 is obtained, following under oxygen saturation state in 0.1M KOH solutions
Ring volt-ampere spectrogram, shows an obvious cathodic reduction peak in saturation oxygen in figure, reduction spike potential is 0.78V, reduction
Peak current is 1.2mA, and Fig. 6 is metal-nitrogen-doped carbon material that example 2 is obtained, the oxygen saturation state in 0.1M KOH solutions
Under polarization curve, rise spike potential reach 1.04V, half wave potential reach 0.88V, hence it is evident that higher than platinum carbon catalyst, show catalyst pair
Hydrogen reduction has good catalytic effect.
Fig. 7 is metal-nitrogen-doped carbon material graph of pore diameter distribution that example 2 is obtained, it can be seen that material has micropore and Jie
Hole Liang Zhong apertures, mesopore diameter is in 30nm or so.Fig. 8 is charge and discharge cycles curve, it can be seen that 34mA g-1Electricity
Under current density, after 100 times circulate, capacity is held essentially constant.
Embodiment 3
A kind of preparation method of metal-nitrogen-doped carbon material, operating procedure is as follows：
(1) ethanol solution for taking 50ml is placed in two mouthfuls of flasks equipped with condensation return pipe, adds 2,6- diacetyls
Pyridine 1mol, is stirred at room temperature 10 minutes, adds 2,4- diaminourea -6- methyl isophthalic acids, and 3,5- triazine 1mol are stirred at room temperature 10 points
Clock, under nitrogen protection, after being heated to 50 DEG C from room temperature, adds oxalic acid 0.1g, continues stirring reaction 24 hours, in course of reaction
There is dehydrating condensation in acyl group, form many flute profile iminopyridine ligand polymers with metal ion complexation ability with amino,
Naturally cool to room temperature；
(2) Dehydrated nickel chloride 0.5mol g are taken, is dissolved in 10ml absolute ethyl alcohols, nickel to be chlorinated is completely dissolved completely, one
Secondary property will be dissolved with during the 10ml ethanol solutions of Dehydrated nickel chloride are added to step (1) and contain iminopyridine ligand polymer
In two mouthfuls of flasks of thing, reaction 12 hours is stirred at room temperature, forms the polymer with metal ion, reaction resulting solution is placed in
In forced air drying, after 80 DEG C of dryings 5 hours, it is placed in vacuum drying chamber, 80 DEG C of dryings 10 hours obtain metal ion polymer
Powder；
(3) step (2) gained metal ion polymer powder is ground 10 minutes, being subsequently placed in tube furnace carries out hot tearing
Solution treatment, that is, after being passed through nitrogen 30 minutes, 750 DEG C are heated to from room temperature with 10 DEG C/min, are incubated 2 hours, naturally cool to room
Temperature；Gained material is taken out into grinding 10 minutes, is put into the 0.5mol/L sulfuric acid solutions of 500ml, 80 DEG C of stirrings are carried out for 10 hours
Pickling, is cooled to room temperature, and suction filtration is separated, and is cleaned with deionized water more than 8 times, 100 DEG C of dryings 12 hours in vacuum drying chamber,
Being placed in again in tube furnace carries out secondary thermal cracking treatment, after being passed through nitrogen 30 minutes, 550 is heated to 10 DEG C/min from room temperature
DEG C, process 1 hour, naturally cool to room temperature and obtain product, as metal-nitrogen-doped carbon material.
Fig. 9 is the metal-nitrogen-doped carbon material C V performance maps, the oxygen saturation shape in 0.1M KOH solutions that example 3 is obtained
Cyclic voltammetric spectrogram under state, shows an obvious cathodic reduction peak in saturation oxygen in figure, reduction spike potential is
0.74V, reduction peak current is 1.15mA, shows that metal-nitrogen-doped carbon material has good catalytic effect to hydrogen reduction.
Embodiment 4
A kind of preparation method of metal-nitrogen-doped carbon material, operating procedure is as follows：
(1) acetone soln for taking 50ml is placed in two mouthfuls of flasks equipped with condensation return pipe, adds DAP
1mol, is stirred at room temperature 10 minutes, adds 2,6- diaminopurine 1mol, is stirred at room temperature 10 minutes, under helium gas shielded, from room
After temperature is heated to 100 DEG C, oxalic acid 0.1g is added, continue stirring reaction 24 hours, acyl group is dehydrated with amino in course of reaction
Condensation, forms many flute profile iminopyridine ligand polymers with metal ion complexation ability, naturally cools to room temperature；
(2) waterless cobaltous chloride 1mol is taken, is dissolved in 10ml propyl alcohol, cobalt to be chlorinated is completely dissolved completely, disposably will be molten
The 10ml ethanol solutions that solution has waterless cobaltous chloride are added to two mouthfuls containing iminopyridine ligand polymer in step (1)
In flask, reaction 12 hours is stirred at room temperature, forms the polymer with metal ion, reaction resulting solution is placed in forced air drying
In, after 80 DEG C of dryings 5 hours, it is placed in vacuum drying chamber, 80 DEG C of dryings 10 hours obtain metal ion polymer powder；
(3) step (2) gained metal ion polymer powder is ground 10 minutes, being subsequently placed in tube furnace carries out hot tearing
Solution treatment, that is, after being passed through helium 30 minutes, 750 DEG C are heated to from room temperature with 10 DEG C/min, are incubated 2 hours, naturally cool to room
Temperature；Gained material is taken out into grinding 10 minutes, is put into the 0.5mol/L sulfuric acid solutions of 500ml, 80 DEG C of stirrings are carried out for 10 hours
Pickling, is cooled to room temperature, and suction filtration is separated, and is cleaned with deionized water more than 8 times, 100 DEG C of dryings 12 hours in vacuum drying chamber,
Being placed in again in tube furnace carries out secondary thermal cracking treatment, after being passed through nitrogen 30 minutes, 600 is heated to 10 DEG C/min from room temperature
DEG C, process 2 hours, naturally cool to room temperature and obtain product, as metal-nitrogen-doped carbon material.
Products obtained therefrom is applied to super capacitor：Figure 10 is metal-nitrogen-doped carbon material that example 4 is obtained, in 0.5M H2SO4
In solution, the cyclic voltammetric spectrogram under nitrogen saturation state shows a larger chemical electric capacity in saturation oxygen in figure
Area, electrochemical capacitor is 193F g-1, show that metal-nitrogen-doped carbon material has preferable electric capacity.
Embodiment 5
A kind of preparation method of metal-nitrogen-doped carbon material, operating procedure is as follows：
(1) ethanol solution for taking 40ml is placed in two mouthfuls of flasks equipped with condensation return pipe, adds 2,6- diacetyls
Pyridine 1mol, is stirred at room temperature 10 minutes, adds 2,6 diamino-pyridine 1mol, is stirred at room temperature 10 minutes, under nitrogen protection,
After being heated to 50 DEG C from room temperature, the acetic acid 30 for adding mass concentration to be 37% drips, and continues stirring reaction 12 hours, in course of reaction
There is dehydrating condensation in acyl group, form many flute profile iminopyridine ligand polymers with metal ion complexation ability with amino,
Naturally cool to room temperature；
(2) frerrous chloride 5mol is taken, is dissolved in 10ml absolute ethyl alcohols, ferrous iron to be chlorinated is completely dissolved completely, disposably
The 10ml ethanol solutions of frerrous chloride will be dissolved with to be added to containing iminopyridine ligand polymer two in step (1)
In mouthful flask, reaction 12 hours is stirred at room temperature, forms the polymer with metal ion, reaction resulting solution is placed in air blast and does
In dry, after 80 DEG C of dryings 5 hours, it is placed in vacuum drying chamber, 80 DEG C of dryings 10 hours obtain metal ion polymer powder；
(3) step (2) gained metal ion polymer powder is ground 10 minutes, being subsequently placed in tube furnace carries out hot tearing
Solution treatment, that is, after being passed through nitrogen 30 minutes, 1050 DEG C are heated to from room temperature with 8 DEG C/min, are incubated 1 hour, naturally cool to room
Temperature；Gained material is taken out into grinding 10 minutes, is put into the 0.5mol/L sulfuric acid solutions of 500ml, 80 DEG C of stirrings are carried out for 10 hours
Pickling, is cooled to room temperature, and suction filtration is separated, and is cleaned with deionized water more than 8 times, 80 DEG C of dryings 8 hours in vacuum drying chamber, then
Being placed in tube furnace carries out secondary thermal cracking treatment, after being passed through nitrogen 30 minutes, 400 DEG C is heated to 8 DEG C/min from room temperature,
Treatment 0.5 hour, naturally cools to room temperature and obtains product, as metal-nitrogen-doped carbon material.
Embodiment 6
A kind of preparation method of metal-nitrogen-doped carbon material, operating procedure is as follows：
(1) ethanol solution for taking 50ml is placed in two mouthfuls of flasks equipped with condensation return pipe, adds 2,6- diacetyls
Pyridine 1mol, is stirred at room temperature 5 minutes, adds 3,3'- diaminobenzidine 1.2mol, is stirred at room temperature 10 minutes, is protected in nitrogen
Under shield, after being heated to 70 DEG C from room temperature, oxalic acid 0.1g is added, continue stirring reaction 24 hours, acyl group and amino in course of reaction
Generation dehydrating condensation, forms many flute profile iminopyridine ligand polymers with metal ion complexation ability, naturally cools to
Room temperature；
(2) anhydrous frerrous chloride 0.5mol is taken, is dissolved in 10ml absolute ethyl alcohols, ferrous iron to be chlorinated is completely dissolved completely,
Disposable being dissolved with during the 10ml ethanol solutions of anhydrous frerrous chloride are added to step (1) contains iminopyridine part
In two mouthfuls of flasks of polymer, reaction 12 hours is stirred at room temperature, forms the polymer with metal ion, resulting solution will be reacted
It is placed in forced air drying, after 80 DEG C of dryings 5 hours, is placed in vacuum drying chamber, 80 DEG C of dryings 10 hours obtains metal ion and gather
Compound powder；
(3) step (2) gained metal ion polymer powder is ground 10 minutes, being subsequently placed in tube furnace carries out hot tearing
Solution treatment, that is, after being passed through nitrogen 30 minutes, 650 DEG C are heated to from room temperature with 7 DEG C/min, are incubated 1 hour, naturally cool to room
Temperature；Gained material is taken out into grinding 10 minutes, is put into the 0.5mol/L sulfuric acid solutions of 500ml, 80 DEG C of stirrings are carried out for 10 hours
Pickling, is cooled to room temperature, and suction filtration is separated, and is cleaned with deionized water more than 8 times, 100 DEG C of dryings 12 hours in vacuum drying chamber,
Being placed in again in tube furnace carries out secondary thermal cracking treatment, after being passed through nitrogen 30 minutes, 500 is heated to 7 DEG C/min from room temperature
DEG C, process 1.5 hours, naturally cool to room temperature and obtain product, as metal-nitrogen-doped carbon material.
Embodiment 7
A kind of preparation method of nitrogen-doped carbon material, operating procedure is as follows：
(1) ethanol solution for taking 50ml is placed in two mouthfuls of flasks equipped with condensation return pipe, adds 2,6- diacetyls
Pyridine 1mol g, are stirred at room temperature 10 minutes, add p-phenylenediamine 0.8mol, (it is stirred at room temperature 10 minutes, under nitrogen protection,
After being heated to 100 DEG C from room temperature, oxalic acid 0.1g is added, continue stirring reaction 24 hours, acyl group occurs with amino in course of reaction
Dehydrating condensation, forms many flute profile iminopyridine ligand polymers with metal ion complexation ability, naturally cools to room temperature；
(2) step (1) many flute profile iminopyridine ligand polymers of gained are placed in forced air drying, 80 DEG C of dryings 5 are small
Shi Hou, is placed in vacuum drying chamber, 80 DEG C of dryings 10 hours, obtains polymer powder；By 10 points of resulting polymers powder mull
Clock, being subsequently placed in tube furnace carries out thermal cracking treatment, that is, after being passed through nitrogen 30 minutes, be heated to 5 DEG C/min from room temperature
9000 DEG C, 2 hours are incubated, naturally cool to room temperature；Gained material is taken out into grinding 10 minutes, the 0.5mol/L of 500ml is put into
In sulfuric acid solution, 80 DEG C of stirrings carry out pickling in 10 hours, are cooled to room temperature, and suction filtration is separated, cleaned with deionized water more than 8 times,
100 DEG C of dryings 12 hours in vacuum drying chamber, then be placed in tube furnace and carry out secondary thermal cracking treatment, it is passed through nitrogen 30 minutes
Afterwards, 500 DEG C are heated to 5 DEG C/min from room temperature, are processed 1 hour, naturally cooled to room temperature and obtain product, as nitrogen-doped carbon
Material.
Embodiment 8
A kind of preparation method of nitrogen-doped carbon material, operating procedure is as follows：
(1) butanol solution for taking 50ml is placed in two mouthfuls of flasks equipped with condensation return pipe, adds DAP
1mol, is stirred at room temperature 10 minutes, adds p-phenylenediamine 1mol, is stirred at room temperature 10 minutes, under nitrogen protection, from room temperature heating
To after 80 DEG C, acetic acid 0.5mlg is added, continues stirring reaction 24 hours, acyl group occurs dehydrating condensation with amino in course of reaction,
The many flute profile iminopyridine ligand polymers with metal ion complexation ability are formed, room temperature is naturally cooled to；
(2) step (1) many flute profile iminopyridine ligand polymers of gained are placed in forced air drying, 80 DEG C of dryings 5 are small
Shi Hou, is placed in vacuum drying chamber, 80 DEG C of dryings 10 hours, obtains polymer powder；By 10 points of resulting polymers powder mull
Clock, being subsequently placed in tube furnace carries out thermal cracking treatment, that is, after being passed through nitrogen 30 minutes, be heated to 5 DEG C/min from room temperature
900 DEG C, 2 hours are incubated, naturally cool to room temperature；Gained material is taken out into grinding 10 minutes, the 0.5mol/L sulphur of 500ml is put into
In acid solution, 80 DEG C of stirrings carry out pickling in 10 hours, are cooled to room temperature, and suction filtration is separated, cleaned with deionized water more than 8 times,
100 DEG C of dryings 12 hours in vacuum drying chamber, then be placed in tube furnace and carry out secondary thermal cracking treatment, it is passed through nitrogen 30 minutes
Afterwards, 600 DEG C are heated to 5 DEG C/min from room temperature, are processed 2 hours, naturally cooled to room temperature and obtain product, as nitrogen-doped carbon
Material.
Application example
1st, embodiment 1 is prepared into products obtained therefrom and is applied to oxygen reduction catalyst, that is, take metal-nitrogen co-doped carbon material
10mg, is dispersed in the Nafion ethanol solutions of the 0.1wt% of 1ml, and ice-bath ultrasonic 15min obtains ink shape slurries, takes 15 μ l
Slurries drop to working electrode surface, are uniformly distributed, and spontaneously dry.Electro-chemical test uses working electrode, to electrode, reference electrode
Three-electrode system, reference electrode uses reversible hydrogen electrode, and to electrode using platinized platinum to electrode, platinized platinum area is 1cm2, work
Electrodes use rotating ring disk electrode (r.r.d.e) (a diameter of 5.6mm), and electrolyte is 0.1mol KOH solutions.Cyclic voltammetric is tested, and is swept
Speed is retouched for 50mV s-1Saturation Oxygen Condition in realize, the potential region of scanning is 0-1.15V vs..RHE.Polarization curve
Test, sweep speed is 5mV s-1Saturation Oxygen Condition in, scanning potential region is 0-1.15V vs..RHE, and rotating speed is
1600rpm, test result is Fig. 3 and Fig. 4.
The foregoing description to specific illustrative embodiment of the invention be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explaining that certain principles of the invention and its reality should
With so that those skilled in the art can realize and using a variety of exemplaries of the invention and
A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. the preparation method of a kind of nitrogen or metal-doped carbon material, it is characterised in that comprising following operating procedure：
(1) DAP and the amino monomers of 2 or more than 2 are used, is protected in solvent, catalyst and inert gas
Under conditions of shield, reaction forms iminopyridine ligand polymer；
(2) step (1) gained iminopyridine ligand polymer is carried out into thermal cracking treatment under inert gas shielding, is obtained
Nitrogen-doped carbon material, post processing, obtains final product.
2. preparation method according to claim 1, it is characterised in that：To prepare metal-nitrogen co-doped carbon material, also
Including following operation：To adding slaine to carry out mixed ligand in step (1) gained iminopyridine ligand polymer, tool is formed
There is the polymer of metal ion, be dried to obtain metal ion polymer powder；Metal ion polymer powder will be dried to obtain to exist
Under mixed gas protected, thermal cracking treatment is carried out, obtain metal-nitrogen co-doped carbon material.
3. preparation method according to claim 2, it is characterised in that：Pyrrole in described iminopyridine ligand polymer
The ratio between mole of metal ion in pyridine part mole and slaine is 1：1~2；Described drying temperature is 80~100
DEG C, dry 8~12 hours.
4. preparation method according to claim 2, it is characterised in that：Described slaine is iron, cobalt, nickel, manganese plasma
The chloride of compound, nitrate, sulfate or acetate one or more mixtures.
5. preparation method according to claim 1, it is characterised in that：Solvent described in step (1) is methyl alcohol, ethanol,
N-butanol, propyl alcohol, water, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetylamide, monochloro methane, dichloromethane, three chloromethanes
One or more mixtures in alkane or tetrachloromethane；Described catalyst is the one kind in formic acid, acetic acid or oxalic acid；Institute
The inert gas stated is to close the one kind in nitrogen, argon gas or helium.
6. preparation method according to claim 1, it is characterised in that：Reaction temperature is 50 DEG C~150 DEG C in step (1),
Reaction time is 8~24 hours, is persistently stirred during reaction.
7. preparation method according to claim 1, it is characterised in that：DAP described in step (1)
Amino monomers with 2 or more than 2 are into mol ratio 1:0.8~1.2.
8. preparation method according to claim 1, it is characterised in that：Amino monomers described in step (1) are 2,6- bis-
Adenine phosphate, 6- methyl -2,4- pyrimidinediamines, 2,4- di-amino-pyrimidines, 1,5- naphthylenediamines, DAP, to diamino
Base biphenyl, p-phenylenediamine, melamine, 1,8- diaminonaphthalenes, 4- diazanyls -6- (2- pyridines) -1,3,5-triazines -2- amine, 2,4-
The methyl isophthalic acid of diaminourea -6,3,5- triazines, 2,3,5,6- 4-aminopyridine hydrochlorides, -6 phenyl of 2,4- diaminourea -1,3,5-triazines,
2,4- diaminourea -6- dimethylaminos -1,3,5-triazines, 4,6-, tri- ammonia -1,3,5-triazines, 2,4- diamino-1,3,5-triazines, 2,
One kind in 4- di-amino-pyrimidine -5- nitriles, Isosorbide-5-Nitrae-cyclohexanediamine or 2,6- diaminopyrazine.
9. preparation method according to claim 1, it is characterised in that：Thermal cracking treatment temperature described in step (2) is guarantor
Heating rate is held for 5~10 DEG C/min is warming up to 650~1050 DEG C of high temperature cabonizations 1~2 hour；Mixing described in step (2)
Gas is the mixture of inert gas or inert gas and ammonia, and described inert gas is in nitrogen, argon gas or helium
It is a kind of；Described inert gas is with ammonia according to 1:0.2 volume ratio mixes.
10. preparation method according to claim 1, it is characterised in that：Post processing described in step (2) include pickling,
Cooling, separate, cleaning, 80~100 DEG C of dryings more than 8 hours, then carry out secondary thermal cracking treatment, process time is 0.5~2
Hour, temperature is 400~600 DEG C, that is, obtain product；Wherein, it is the sulfuric acid solution of 0.5mol/L that described pickling uses concentration
Keeping temperature is cleaned 8~12 hours for 80~100 DEG C, is cooled to room temperature, after filtering, is cleaned more than 8 times, or use concentration
For the hydrochloric acid solution of 0.1mol/L is cleaned 12 hours at room temperature, room temperature is cooled to, after filtering, cleaned more than 8 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710056827.8A CN106915735B (en) | 2017-01-25 | 2017-01-25 | Preparation method of nitrogen or metal doped carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710056827.8A CN106915735B (en) | 2017-01-25 | 2017-01-25 | Preparation method of nitrogen or metal doped carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106915735A true CN106915735A (en) | 2017-07-04 |
| CN106915735B CN106915735B (en) | 2020-08-11 |
Family
ID=59453350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710056827.8A Active CN106915735B (en) | 2017-01-25 | 2017-01-25 | Preparation method of nitrogen or metal doped carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106915735B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107308975A (en) * | 2017-07-07 | 2017-11-03 | 江南大学 | A kind of preparation method of nitrogen-doped carbon package metals oxide catalyst |
| CN107694594A (en) * | 2017-10-13 | 2018-02-16 | 荆楚理工学院 | Nitrogen-doped carbon material of immobilized metal and its production and use |
| CN110336044A (en) * | 2019-06-17 | 2019-10-15 | 华中科技大学 | A kind of monatomic fuel battery cathod catalyst of base metal, its preparation and application |
| CN110683530A (en) * | 2019-08-26 | 2020-01-14 | 广西大学 | Method for in-situ synthesis of cobalt-nitrogen co-doped carbon nano tube |
| CN113058651A (en) * | 2019-12-31 | 2021-07-02 | 南京理工大学 | Preparation method of two-dimensional coordination polymer electrocatalyst based on melem derivative |
| CN113318783A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Acidic bread-ring-shaped macroporous mesoporous material, preparation method thereof and application thereof in preparation of 2, 6-bis (imino) pyridine |
| CN115672267A (en) * | 2021-07-27 | 2023-02-03 | 无锡蓝海工程设计有限公司 | Nitrogen-doped carbon material, preparation thereof and application thereof in heavy metal ion adsorption |
| CN115672267B (en) * | 2021-07-27 | 2024-05-17 | 无锡蓝海工程设计有限公司 | Nitrogen-doped carbon material, preparation method thereof and application thereof in heavy metal ion adsorption |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701183A (en) * | 2012-06-05 | 2012-10-03 | 南京航空航天大学 | N-rich mesoporous carbon material and template-free preparation method thereof as well as method for manufacturing working electrode and application of working electrode |
| CN103143378A (en) * | 2013-03-04 | 2013-06-12 | 太原理工大学 | Preparation method of non-noble metal oxygen reduction electrocatalyst for cathode of fuel cell |
| CN103811775A (en) * | 2014-03-06 | 2014-05-21 | 南开大学 | Porous nano composite material for fuel cell oxygen reduction catalyst |
-
2017
- 2017-01-25 CN CN201710056827.8A patent/CN106915735B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701183A (en) * | 2012-06-05 | 2012-10-03 | 南京航空航天大学 | N-rich mesoporous carbon material and template-free preparation method thereof as well as method for manufacturing working electrode and application of working electrode |
| CN103143378A (en) * | 2013-03-04 | 2013-06-12 | 太原理工大学 | Preparation method of non-noble metal oxygen reduction electrocatalyst for cathode of fuel cell |
| CN103811775A (en) * | 2014-03-06 | 2014-05-21 | 南开大学 | Porous nano composite material for fuel cell oxygen reduction catalyst |
Non-Patent Citations (2)
| Title |
|---|
| BROOKE L. SMALL ET AL.: "Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene", 《J. AM. CHEM. SOC.》 * |
| LINGLING FU ET AL.: "Influence of the metal sites of M-N-C(M=Co，Fe，Mn)catalysts derived from metalloporphyrins in ethylbenzene oxidation", 《CHINESE JOURNAL OF CATALYSIS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107308975A (en) * | 2017-07-07 | 2017-11-03 | 江南大学 | A kind of preparation method of nitrogen-doped carbon package metals oxide catalyst |
| CN107694594A (en) * | 2017-10-13 | 2018-02-16 | 荆楚理工学院 | Nitrogen-doped carbon material of immobilized metal and its production and use |
| CN107694594B (en) * | 2017-10-13 | 2021-01-12 | 荆楚理工学院 | Metal-immobilized nitrogen-doped carbon material and preparation method and application thereof |
| CN110336044A (en) * | 2019-06-17 | 2019-10-15 | 华中科技大学 | A kind of monatomic fuel battery cathod catalyst of base metal, its preparation and application |
| CN110683530A (en) * | 2019-08-26 | 2020-01-14 | 广西大学 | Method for in-situ synthesis of cobalt-nitrogen co-doped carbon nano tube |
| CN113058651A (en) * | 2019-12-31 | 2021-07-02 | 南京理工大学 | Preparation method of two-dimensional coordination polymer electrocatalyst based on melem derivative |
| CN113058651B (en) * | 2019-12-31 | 2023-05-05 | 南京理工大学 | Preparation method of two-dimensional coordination polymer electrocatalyst based on melem derivative |
| CN113318783A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Acidic bread-ring-shaped macroporous mesoporous material, preparation method thereof and application thereof in preparation of 2, 6-bis (imino) pyridine |
| CN115672267A (en) * | 2021-07-27 | 2023-02-03 | 无锡蓝海工程设计有限公司 | Nitrogen-doped carbon material, preparation thereof and application thereof in heavy metal ion adsorption |
| CN115672267B (en) * | 2021-07-27 | 2024-05-17 | 无锡蓝海工程设计有限公司 | Nitrogen-doped carbon material, preparation method thereof and application thereof in heavy metal ion adsorption |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106915735B (en) | 2020-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106915735A (en) | A kind of preparation method of nitrogen or metal-doped carbon material | |
| CN105680048B (en) | A kind of anode comprising nitrogen-doped graphene, preparation method and the lithium battery using the anode | |
| Zhao et al. | Bi-interface induced multi-active MCo2O4@ MCo2S4@ PPy (M= Ni, Zn) sandwich structure for energy storage and electrocatalysis | |
| Sheng et al. | High Photocatalytic Oxygen Evolution via Strong Built‐In Electric Field Induced by High Crystallinity of Perylene Imide Supramolecule | |
| Yu et al. | Mesoporous NiCo2O4 nanoneedles grown on 3D graphene-nickel foam for supercapacitor and methanol electro-oxidation | |
| CN105348303B (en) | A kind of porphyrin two dimension covalently organic frame conjugated polymer, its preparation method and application | |
| CN105253871B (en) | Ultracapacitor nitrogenous carbon material and preparation method thereof, electrode material for super capacitor | |
| CN104973596B (en) | A kind of Heteroatom doping hollow ball graphene composite material and preparation method and application | |
| CN102451727B (en) | M/N-C catalyst and preparation and application thereof | |
| CN103956271A (en) | Manganese oxide/graphene porous microspheres, preparation method and energy storage application thereof | |
| Liu et al. | Enhanced methanol oxidation activity of Pt catalyst supported on the phosphorus-doped multiwalled carbon nanotubes in alkaline medium | |
| CN104299798B (en) | A kind of boron atom doping vario-property grapheme material, preparation method and application | |
| CN105390696B (en) | A kind of preparation method of height ratio capacity lithium cell cathode material | |
| CN102516764B (en) | Polyaniline nanowire/ graded porous carbon composite material as well as preparation method and application thereof | |
| CN103854881A (en) | Preparation method for graphene/carbon nano-tube combined electrode | |
| CN101941972A (en) | Preparation method of lanthanide sandwich-type phthalocyanine complex and application of lanthanide sandwich-type phthalocyanine complex in Li/SOC12 cell | |
| CN108199055A (en) | Nitrogen co-doped carbon supported platinum catalyst of a kind of boron and preparation method thereof | |
| Gu et al. | A g-C3N4 self-templated preparation of N-doped carbon nanosheets@ Co-Co3O4/Carbon nanotubes as high-rate lithium-ion batteries’ anode materials | |
| CN110137516A (en) | The sulfur and nitrogen co-doped carbon elctro-catalyst and preparation method of ferro-tin alloy load | |
| CN104979568A (en) | Fuel cell cathode catalyst and preparation method thereof | |
| CN105152160A (en) | Preparation method of nitrogen-doped carbon microspheres | |
| CN104505523A (en) | Platinum-based catalyst/graphene composite material and preparation method thereof | |
| CN104707640A (en) | Non-noble metal oxygen reduction catalyst, and preparation method and application thereof | |
| CN107326393B (en) | A kind of preparation method of water power parsing oxygen non-precious metal catalyst | |
| Liu et al. | Improving the performance of negative electrode for vanadium redox flow battery by decorating bismuth hydrogen edetate complex on carbon felt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Tian Zhiqun Inventor after: Zhang Xiaoran Inventor after: Shen Peikang Inventor after: Liu Zong Inventor after: Lv Dandan Inventor after: Liang Lizhe Inventor after: Yin Shibin Inventor before: Tian Zhiqun Inventor before: Liu Zong Inventor before: Shen Peikang Inventor before: Zhang Xiaoran Inventor before: Lv Dandan Inventor before: Liang Lizhe Inventor before: Yin Shibin |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |